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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008

Lecture #26-27

page 1

STATISTICAL THERMODYNAMICS
Calculation of macroscopic thermodynamic results Entropically driven examples:

Free expansion of a gas

V1 gas

vacuum

V2 gas

Lattice model for ideal gas translation: Molecular volume v, Total volume V All molecular positions have equal energy trans = 0 All system microstates have equal energy Etrans = 0 Calculate S = k ln in each state Molecular degeneracy g = V/v
System degeneracy = gN/N! = (V/v)N/N!
For expansion from volume V1 to V2,
V1 V2

(V v ) N! S = kln 2 kln 1 = kln 2 = kln 2 N 1 (V1 v ) N! S = Nkln V2 V = nRln 2 V1 V1 V2 V1

Should look familiar! And G = H TS = nRTln

Entropy change is positive, free energy change is negative, as we expect.

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Ideal gas mixture

NA VA

NB VB

N = N A + NB
V = VA + VB

Assume same initial (p,T) for A & B same (p,T) for mixture Assume equal molecular volumes & lattice cell sizes. Then initially S1 = kln A + kln B = kln AB

(V v ) (VB v ) = kln A
NA

NB

NA !

NB !

After mixing: Count how many ways to distribute NA molecules of A and NB molecules of B among the (V/v) lattice sites As before, the number of ways to distribute N
molecules among (V/v) sites is (V/v)N.
To correct for indistinguishability, divide by NA!NB!
So the final state entropy is
S2

(V v ) = kln = kln

NA !NB !
N

S = S2 S1

(V v ) = kln

NA !NB !

(V v ) (VB v ) kln A
NA

NB

NA !

NB !

( ) V v) ( = kln N N (VA v ) (VB v )

NA + NB
A

= kln

V NA V NB NA NB VA VB

Since the initial pressures are the same, the initial volumes must be in the ratio of the number of molecules, i.e. VA/V = NA/N = XA and VB/V = XB, so V NA V NB NB NA S = kln NA NB = kln XA kln XB = Nk ( XA ln XA + XB ln XB ) VA VB (> 0)

With a simple microscopic model we can derive the macroscopic entropy change!

5.60 Spring 2008

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Ideal liquid mixture Lattice model is different from gas because all the cells are occupied. Then in the pure liquid there is no disorder at all!

SA = kln A = kln1 = 0
+

SB = kln B = kln1 = 0
Mixture: N molecules for N sites.
First molecule has N choices, second (N 1), etc.
# ways to put the molecules into sites = N!
Correct for overcounting by dividing by NA!NB!
Smix = Smix ( SA + SB ) = Smix = kln mix = kln N! NA !NB !

Stirlings approximation lnN! NlnN N

Smix = Nkln N Nk NAklnNA NAk + NBkln NB NBk = ( NA + NB ) kln N NAkln NA NBkln NB = NAkln = Nk ( XA ln XA + XB ln XB )

N N + NBkln NA NB

Real liquid has additional states - positional disorder, molecular rotation, etc. but these occur in both the pure and mixed liquids, so Smix is dominated by the disorder in molecular positions that the lattice model describes reasonably well. *********************************************************************** Combinatorics: Simple example Mix 2 molecules A + 3 molecules B = 10 = 5!/2!3!

How many distinct configurations ?

5.60 Spring 2008

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Energy & entropy changes We saw one example earlier, with 4-segment polymers.

Molecular state:

Energy : Degeneracy g:

0 1

int

int 3

int

Weve redefined the zero of energy as the ground state energy. Configurational molecular partition function is
qconf = =

e states

i
i

i,conf kT

= e 0 kT + e

int kT

+ e int

kT

+ e int

kT

ge energy levels
i

i kT

= e 0 kT + 3e

int kT

= 1 + 3e

int kT

For a solution of noninteracting polymer molecules,

N Qconf = qconf = 1 + 3e

int kT

We can determine the thermodynamic properties: Aconf = kT ln Qconf = NkT ln 1 + 3e

int kT

) = NkT ln (1 + 3e
) V,N

int

Uconf

ln 1 + 3e int ln Qconf = = N V,N

3 e int = N int 1 + 3e int

Energy scales with N: molecules are not interacting with each other so total energy is just a sum of individual molecule energies.

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Average energy per molecule is

conf = Uconf 3int e int = N 1 + 3e int

But we also know = iP i =

i

e
i i

0 + 3int e int 1 + 3e int

- same result

Sconf

Aconf Uconf 1 ln Qconf N 3int e int int = + = kln Qconf + = Nkln 1 + 3e T T T V,N T 1 +
3e
int

Also scales with N sum over individual molecule entropy contributions Average molecular configurational entropy is
sconf = kln 1 + 3e

int

1 3int e int T 1 + 3e int

In high-T (low-) limit, its kln(4) as expected. In low-T limit, its kln(1) = 0.

ln Q A conf = = kT ln 1 + 3e int = kT N T,V N T,V

Chemical potential is just A per molecule, and A scales with N so its just A/N. CVconf
1 Uconf N 3int e int
Uconf = = kT 2 = kT 2 int T V,N V,N 1 + 3e

3
N 1 + 3e = int2 kT

int

) (

int

)e (1 + 3e )
e
int int

int
2

( 3

int

int

Scales with N, so we can think of a configurational heat capacity per molecule. Complicated function, but its limits are understandable:

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CVconf 0 as T 0 At low T, all molecules are in the lowest state. If kT increases infinitesimally, all the molecules are still in the lowest state! So the configurational energy Uconf doesnt change!

int

Low-T limit kT

CVconf 0 as T At high T, the molecules are equally distributed among all the states. If kT increases, they are still equally distributed among all the states! So Uconf doesnt change.

kT High-T limit

int

The low-T limit CV 0 is common to almost every degree of freedom since ultimately a temperature is reached at which only the lowest level is occupied. The high-T limit CV 0 is characteristic of systems or degrees of freedom with a finite number of states, i.e. a maximum possible energy. In that case, ultimately a temperature is reached at which the equilibrium distribution is ~ equal probability of all the levels being occupied. This is the case for molecular configurations as discussed here and for spin states of nuclei and electrons.